Exciton Binding Energy Research Articles

A computational investigation of the effects of changes of donor–acceptor linker length and acceptor on electronic spectra of small-molecule single-component organic solar cells

Small-molecule single-component organic solar cells (SM-SCOSCs) have great potential for commercial application. However, the effects of changes of donor–acceptor linker length and acceptor unit of small molecules of active layers on their photoelectric properties are still not well understood. In this work, four state-of-the-art dyads 1–4 were selected to investigate these effects since dyad 4 created the highest power conversion efficiency (PCE) of 5.34% of SM-SCOSC; and their electronic structures were investigated. The results indicate that increasing the length of the donor–acceptor connecting bridge leads to a decrease in exciton binding energy, and so does replacing the acceptor component PC61BM with PC71BM. Furthermore, the simulated electronic absorption spectrum of dyad 4 is enhanced with respect to others. We also find that the introduction of PC71BM creates more channels for transitions from local excited states to charge transfer states. This work gains a deep insight into the relationship between molecular structure and performance of SM-SCOSC.

Mechanistic Insights into the Photoluminescence Enhancement in Surface Ligand Modified CsPbBr3 Perovskite Nanocrystals.

We report a mechanistic study of the photoluminescence (PL) enhancement in CsPbBr3 perovskite nanocrystals (PNCs) induced by organic/inorganic hybrid ligand engineering. Compared to the as-synthesized oleic acid-oleylamine modified PNCs, the tributylphosphine oxide-CaBr2 modified PNCs can achieve a better passivation effect due to strong P═O-Pb coordination and Br-vacancy remedy, resulting in enhanced PL efficiency. We employ steady-state/time-resolved/temperature-dependent PL and fluence/polarization-dependent ultrafast transient absorption spectroscopy to obtain a mechanistic understanding of such an enhancement effect from both nonradiative and radiative perspectives. As for the dominating nonradiative recombination suppression, we quantitatively evaluate the contributions from channels of exciton dissociation and exciton trapping, which are connected to exciton binding energy and activation energy of exciton trapping to surface defect-induced trap states, respectively. We also look into the radiative recombination enhancement, which is likely due to the increase in electron-hole overlap of photogenerated excitons induced by slight Ca-doping. These mechanistic insights would be of guiding value for perovskite-based light-emitting applications.

Vertical Graphene/Pentacene Single Crystal/Graphene Transistors for Self‐Powered Weak Light Detection and High‐Speed Imaging

AbstractOrganic semiconductors are promising candidates for next‐generation photodetectors owing to their unique properties including large absorption coefficient and intrinsic mechanical flexibility. However, limited by high defect density, large exciton binding energy, and short exciton diffusion length, many challenges remain for fabricating high‐performance organic photodetectors, especially for scenarios where weak light sensing and high‐speed imaging are required. Herein, by coupling single‐crystal pentacene with monolayer graphene, a vertical organic phototransistor with excellent zero‐bias photon detecting capacity is demonstrated. Under self‐powered weak light condition, the responsivity and specific detectivity are 2.86 AW−1 and 3.3 × 1011 Jones (based on experiment spectral noise density), respectively. It is demonstrated that weak light down to 25 nWcm−2 can be detected. When operating with an external bias, the responsivity of the device increases dramatically (up to 105 AW−1), and a better 3 dB bandwidth (≈74 kHz) is obtained. Finally, imaging functionality is demonstrated by employing this vertical transistor as a single‐sensing pixel. This work suggests organic single crystals exhibit enormous potential in advanced optoelectronic systems, and may provide a viable route for weak light detecting and high‐speed imaging.

Temperature‐Dependent Excitonic Band Gap in Lead‐Free Bismuth Halide Low‐Dimensional Perovskite Single Crystals

AbstractIn this study, the optical behavior of lead‐free Bi‐based low‐dimensional perovskite single crystals (Cs3Bi2Cl9, Cs3Bi2Br9, Cs3Bi2I9, and MA3Bi2I9) is investigated by spectroscopic ellipsometry, supported by X‐ray diffraction and density functional theory calculations. All materials exhibit a strong excitonic peak resulting from photogenerated electron–hole Coulomb interactions, whereas the threshold of continuous absorption is found at higher energies. The resonances of the excitonic and continuous bands, along with exciton binding energies, are extracted through Critical Point Analysis of the ellipsometric data over a wide temperature range (from −90 °C to 90 °C), revealing subtle variations in the optical characteristics for each single crystal. These materials can be applied in optoelectronics as photodetectors because of their high stability and lower toxicity compared to their Pb‐based perovskites.

End-capped engineering of Quinoxaline core-based non-fullerene acceptor materials with improved power conversion efficiency

Improving the light-harvesting efficiency and boosting open circuit voltage are crucial challenges for enhancing the efficiency of organic solar cells. This work introduces seven new molecules (SA1-SA7) to upgrade the optoelectronic and photovoltaic properties of Q-C-F molecule-based solar cells. All recently designed molecules have the same alkyl-substituted Quinoxaline core and CPDT donor but vary in the end-capped acceptor subunits. All the investigated molecules have revealed superior properties than the model (R) by having absorbance ranging from 681 nm to 782 nm in the gaseous medium while 726 nm–861 nm in chloroform solvent, with the lowest band gap ranging from 1.91 to 2.19 eV SA1 molecule demonstrated the highest λmax (861 nm) in chloroform solvent and the lowest band gap (1.91 eV). SA2 molecule has manifested highest dipole moment (4.5089 D), lower exciton binding energy in gaseous (0.33 eV) and chloroform solvent (0.47 eV), and lower charge mobility of hole (0.0077693) and electron (0.0042470). At the same time, SA7 showed the highest open circuit voltage (1.56 eV) and fill factor (0.9166) due to solid electron-pulling acceptor moieties. From these supportive outcomes, it is inferred that our computationally investigated molecules may be promising candidates to be used in advanced versions of OSCs in the upcoming period.

Observation of Multi-Phonon Emission in Monolayer WS2 on Various Substrates.

Transition metal dichalcogenides (TMDs) have unique absorption and emission properties that stem from their large excitonic binding energies, reduced-dielectric screening, and strong spin-orbit coupling. However, the role of substrates, phonons, and material defects in the excitonic scattering processes remains elusive. In tungsten-based TMDs, it is known that the excitons formed from electrons in the lower-energy conduction bands are dark in nature, whereas low-energy emissions in the photoluminescence spectrum have been linked to the brightening of these transitions, either via defect scattering or via phonon scattering with first-order phonon replicas. Through temperature and incident-power-dependent studies of WS2 grown by CVD or exfoliated from high-purity bulk crystal on different substrates, we demonstrate that the strong exciton-phonon coupling yields brightening of dark transitions up to sixth-order phonon replicas. We discuss the critical role of defects in the brightening pathways of dark excitons and their phonon replicas, and we elucidate that these emissions are intrinsic to the material and independent of substrate, encapsulation, growth method, and transfer approach.

Wigner-Seitz truncated time-dependent density functional theory approach for the calculation of exciton binding energies in solids

Wigner-Seitz truncated time-dependent density functional theory approach for the calculation of exciton binding energies in solids

Circular dichroism in two-dimensional BC6N and B3C2N3 in absence of intervalley excitonic coupling

Two-dimensional (2D) noncentrosymmetric systems offer potential opportunities for exploiting the valley degrees of freedom for advanced information processing, owing to non-zero Berry curvature. However, such valley polarization in 2D materials is crucially governed by the intervalley excitonic scattering in momentum space due to reduced electronic degrees of freedom and consequent enhanced electronic correlation. Here, we study the valley excitonic properties of two 2D noncentrosymmetric complementary structures, namely, BC6N and B3C2N3 using first principles-based GW calculations combined with the Bethe–Salpeter equation, that brings the many-body interactions among the quasiparticles. The k-resolved oscillator strength of their first bright exciton indicates their ability to exhibit valley polarization under the irradiation of circularly polarized light of different chiralities. Both the systems show significant singlet excitonic binding energies of 0.74 eV and 1.31 eV, respectively. Higher stability of dark triplet excitons as compared to the singlet one can lead to higher quantum efficiency in both the systems. The combination of large excitonic binding energies and the valley polarization ability with minimal intervalley scattering make them promising candidates for applications in advanced optical devices and information storage technologies.

Significant contributions of second-order exchange terms in GW electron–hole interaction kernel for charge-transfer excitations

The GW electron–hole interaction kernel, which includes two second-order exchange terms in addition to the first-order direct and exchange terms considered in the conventional GW + Bethe–Salpeter method, is applied to 10 two-molecular systems and six thermally activated delayed fluorescence (TADF) molecules in which inter- and intramolecular charge transfer excitations are expected to occur. The contributions of the two second-order exchange terms are almost zero for intermolecular charge transfer excitations and ∼0.75 eV for intramolecular charge transfer excitations according to our exciton analysis method with exciton wave functions. For TADF molecules, we found that the second-order exchange terms are more significant than the first-order exchange terms, and the contributions—even for local-type and delocalized-type excitations—are not negligibly small. We revealed that the two second-order exchange terms are proportional to the molecular size, the exciton binding energy, and the electron–hole overlap strength for intramolecular charge-transfer excitations. We believe that our findings are indispensable for further considerations of the GW method in the future.

Impact of alkaline earth metal doping on the structural, electronic, and optical properties of all inorganic lead-free CsSnX3 (X = I, Br) perovskites: a first-principles study

Recently, researchers have focused on developing more stable, Pb-free perovskites with improved processing efficiency and notable light harvesting ability. In this regard, Sn-based (Sn-b) perovskites have gained considerable interest in developing eco-friendly perovskite solar cells (PSCs). However, the oxidation of Sn2+ to Sn4+ deteriorates the performance of Sn-b PSCs. Nevertheless, this issue could be mitigated by doping alkaline earth (AE) metal. Herein, we have studied the significance of AE doping on CsSnX3 (X = Br, I) perovskites using density functional theory based calculations. The structural, electronic, and optical properties of CsAE y Sn1−y X3 (y = 0, 0.25; AE = Be, Mg, Ca, Sr) compounds were systematically investigated to explore potential candidate materials for photovoltaic applications. Formation energy calculations suggested that the synthesis of other AE-doped compounds is energetically favorable except for the Be-doped compounds. The band gaps of the materials were calculated to be in the range of 0.12–1.02 eV using the generalized gradient approximation. Furthermore, the AE doping considerably lowers the exciton binding energy while remarkably enhancing the optical absorption of CsSnX3, which is beneficial for solar cells. However, in the case of Be and Mg doping, an indirect band gap is predicted. Our theoretical findings demonstrate the potential of executing AE-doped perovskites as absorber material in PSCs, which could deliver better performance than pristine CsSnX3 PSCs.

Structural Tailoring the Phenylenediamine Isomers to Obtain 2D Dion–Jacobson Tin Perovskite Solar Cells with Record Efficiency

Abstract2D Dion–Jacobson (DJ) tin halide perovskite shows impressive stability by introducing diamine organic spacer. However, due to the dielectric confinement and uncontrollable crystallization process, 2D DJ perovskite usually exhibits large exciton binding energy and poor film quality, resulting in unfavorable charge dissociation, carrier transport and device performance. Here, the ortho‐, meta‐, and para‐isomers of phenylenediamine (PDA) are designed for 2D DJ tin halide perovskites. Theoretical simulation and experimental characterizations demonstrate that compared with p‐PDA and m‐PDA, o‐PDA shows larger dipole moment, which further reduces the exciton binding energy for the 2D perovskites. Besides, there is a strong hydrogen bond interaction between o‐PDA cation and inorganic octahedron, which not only improves the structural stability, but also induces larger aggregates in the precursor to form dense and uniform high‐quality films, and strengthens the antioxidant barrier. More interestingly, femtosecond transient absorption further proves that o‐PDA organic spacers can reduce unfavorable small n‐phases, resulting in sufficient and effective charge transfer between different n‐value. As a result, the 2D DJ (o‐PDA)FA3Sn4I13 solar cells achieve a record power conversion efficiency of 7.18%. The study furnishes an effective method to optimize the carrier transport and device performance by tailoring the chemical structure of organic spacers.

Crystal Growth Regulation of Ruddlesden-Popper Perovskites via Self-Assembly of Semiconductor Spacers for Efficient Solar Cells.

The crystal growth and orientation of two-dimensional (2D) perovskite films significantly impact solar cell performance. Here, we incorporated robust quadrupole-quadrupole interactions to govern the crystal growth of 2D Ruddlesden-Popper (RP) perovskites. This was achieved through the development of two unique semiconductor spacers, namely PTMA and 5FPTMA, with different dipole moments. The ((5FPTMA)0.1 (PTMA)0.9 )2 MAn-1 Pbn I3n+1 (nominal n=5, 5F/PTMA-Pb) film shows a preferred vertical orientation, reduced grain boundaries, and released residual strain compared to (PTMA)2 MAn-1 Pbn I3n+1 (nominal n=5, PTMA-Pb), resulting in a decreased exciton binding energy and reduced electron-phonon coupling coefficients. In contrast to PTMA-Pb device with an efficiency of 15.66 %, the 5F/PTMA-Pb device achieved a champion efficiency of 18.56 %, making it among the best efficiency for 2D RP perovskite solar cells employing an MA-based semiconductor spacer. This work offers significant insights into comprehending the crystal growth process of 2D RP perovskite films through the utilization of quadrupole-quadrupole interactions between semiconductor spacers.

Crystal Growth Regulation of Ruddlesden–Popper Perovskites via Self‐Assembly of Semiconductor Spacers for Efficient Solar Cells

AbstractThe crystal growth and orientation of two‐dimensional (2D) perovskite films significantly impact solar cell performance. Here, we incorporated robust quadrupole‐quadrupole interactions to govern the crystal growth of 2D Ruddlesden–Popper (RP) perovskites. This was achieved through the development of two unique semiconductor spacers, namely PTMA and 5FPTMA, with different dipole moments. The ((5FPTMA)0.1(PTMA)0.9)2MAn−1PbnI3n+1 (nominal n=5, 5F/PTMA−Pb) film shows a preferred vertical orientation, reduced grain boundaries, and released residual strain compared to (PTMA)2MAn−1PbnI3n+1 (nominal n=5, PTMA−Pb), resulting in a decreased exciton binding energy and reduced electron‐phonon coupling coefficients. In contrast to PTMA−Pb device with an efficiency of 15.66 %, the 5F/PTMA−Pb device achieved a champion efficiency of 18.56 %, making it among the best efficiency for 2D RP perovskite solar cells employing an MA‐based semiconductor spacer. This work offers significant insights into comprehending the crystal growth process of 2D RP perovskite films through the utilization of quadrupole‐quadrupole interactions between semiconductor spacers.

Dependence of Exciton Binding Energy on Bandgap of Organic Semiconductors.

Strongly bound excitons crucially affect the operation of organic optoelectronic devices. Nevertheless, precise experimental data on the exciton binding energy of organic semiconductors are lacking. In this study, we determine the exciton binding energy as the difference between the optical and transport bandgaps with a precision of 0.1 eV. In particular, electron affinities with a precision higher than 0.05 eV determined by low-energy inverse photoelectron spectroscopy allow us to determine the transport gap and the exciton binding energies with such high precision. Through a systematic comparison of a wide range of organic semiconductors, including 42 organic solar cell materials (15 nonfullerene acceptors, 4 fullerene acceptors, 13 low-bandgap polymers, 7 organic light-emitting diode materials, and 3 crystalline materials), we found that the exciton binding energy is one-quarter of the transport gap regardless of the materials. We interpret this unexpected relation from a hydrogen atom-like model, i.e., the quantized energy levels in a Coulomb potential between the positive and the negative charges.

Dielectric Screening and Charge-Transfer in 2D Lead-Halide Perovskites for Reduced Exciton Binding Energies.

Layered lead-halide perovskites have shown tremendous success as an active material for optoelectronics. This is attributed to the electronic structure of the inorganic sublattice and large exciton binding energies due to quantum and dielectric confinement. Expanding functionalities for applications that depend on free-carrier generation requires new material design routes to decrease the binding energy. Here we use electronic structure methods with model Bethe-Salpeter equation (BSE) to examine the contributions of the dielectric screening and charge-transfer excited-states to the exciton binding energy of phenylethylammonium (PEA2PbBr4) and naphthlethylammonium (NEA2PbBr4) lead-bromide perovskites. Our model BSE calculations show that NEA introduces hole acceptor states which impose charge-transfer character on the exciton along with larger dielectric screening. This substantially decreases the exciton binding compared to PEA. This result suggests the use of organic cations with high dielectric screening and hole acceptor states as a viable strategy for reducing exciton binding energies in two-dimensional halide perovskites.

Dielectric Regulation for Efficient Top-Emission Perovskite Light-Emitting Diodes with Suppressed Efficiency Roll-off.

Perovskite light-emitting diodes (PeLEDs) have shown incalculable application potential in the fields of next-generation displays and light communication owing to the rapidly increased external quantum efficiencies (EQEs). However, most PeLEDs obtain a maximum EQE at small current density (J) region and suffer from severe efficiency roll-off in different extents. Herein, it is demonstrated that the dopant with large dipole moment like KBF4 facilitates the effective dielectric regulation of perovskite emissive layer. The increased dielectric constant lowers the exciton binding energy and suppresses the Auger recombination of the 2D/3D segregated perovskite structure, which improves the photoluminescence quantum yield remarkably at an excitation intensity up to 103mWcm-2. Accordingly, the top-emission PeLED that delivers a high maximum EQE above 20% is fabricated and can retain EQE>10% at an extremely high J of 708mAcm-2. These results represent one of the most efficient top-emission PeLEDs with ultra-low efficiency roll-off, which provide a viable methodology for tuning the dielectric response of perovskite films for improved high radiance performance of perovskite electroluminescence devices.

Unlocking structural and photoelectric properties of lead-free double perovskites at high temperature

The lead-free double perovskite, increasingly sought for optoelectronic pursuits, is distinguished by its notable stability, optical properties, and non-toxic characteristic. An extensive inquiry into the structural and photoelectric properties of Cs2NaBiCl6 at heightened temperatures was undertaken using experimental evaluations and theoretical computations. The compound Cs2NaBiCl6, synthesized using a hydrothermal technique, was confirmed via various analytical methods. Advanced techniques such as high-temperature X-ray diffraction, X-ray fluorescence, X-ray photoelectron spectroscopy, and selected area electron diffraction were employed for the investigation of its crystal structure. Further investigation of microstructure was undertaken using electron microscopes. High-temperature luminescence stability disclosed a high exciton binding energy of 326 meV. The Huang-Rhys factor (6.4) denotes a robust electron-phonon coupling effect and facile formation of self-trapped excitons (700 nm). Applied first principles render valuable insight into structural and photoelectric nuances, notably at escalated temperatures. Cs2NaBiCl6 as an indirect bandgap semiconductor and details the experimental and theoretical bandgap, which exhibits an increasing trend before subsequently declining at elevated temperatures. These results strongly support the material's high-temperature stability, emphasizing its applicability in applications such as rare-earth-doped phosphors. The dynamic stability of the material, evidenced by its mechanical performance, further underscores its potential for application in photoelectric devices.

Importance of nonuniform Brillouin zone sampling for ab initio Bethe-Salpeter equation calculations of exciton binding energies in crystalline solids

Importance of nonuniform Brillouin zone sampling for <i>ab initio</i> Bethe-Salpeter equation calculations of exciton binding energies in crystalline solids

Single-atomic Co-N site modulated exciton dissociation and charge transfer on covalent organic frameworks for efficient antibiotics degradation via peroxymonosulfate activation

Covalent organic framework (COF) materials have received extensive attention in the field of photocatalysis in recent years, but the strong exciton effect in COF has seriously affected the separation of electron-hole pairs so that limiting the enhancement of the photocatalytic performance. It is of great significance to explore suitable ways to regulate the exciton behavior in COF materials and enhance their electron-hole's separation efficiency. By anchoring Co single-atoms within a silver birch leaf-like COF framework (COF-Cox), the exciton in COF is effectively dissociated by forming Co-N sites, producing massive free electrons and holes. Co-N sites also facilitate photogenerated holes aggregation toward Co single-atoms, which effectively drives the carriers' separation in COF framework. The carrier concentration of COF-Co10 is 2.81 times higher compared with the original COF. The reduced exciton binding energy (Eb) further proves that the the formation of Co-N sites promote the exciton dissociation. Consequently, COF-Cox can well activate peroxymonosulfate (PMS) to degrade tetracycline (TC) pollutants, the reaction rate constant of COF-Co10 (3.65 × 10-2 min−1) is 5.27 times higher than COF (6.93 × 10-3 min−1). The possible activation routes and degradation products of TC are also discussed. This study provides a more comprehensive understanding of the exciton behavior for the design of more efficient COF-based catalysts.

Impact of polypyrrole units (pyr*n; n=3, 5, 7, or 9) on the adsorption and excitation dynamics of enrofloxacin antibiotic interaction with hafnium-doped graphene/boron nitride (Hf@GP/BN) heterostructure: A theoretical perspective

This research work focuses on investigating on influence of pyrrole units (pyr) on the structural stability, reactivity, adsorption potential, bonding variation, and the visible-light interactions of enrofloxacin (xacin) antibiotic with hafnium-doped graphene/boron nitride (Hf@GP_BN) heterostructure within the framework of hybrid exchange-correlation functional and the Monte Carlo molecular simulations. The interaction of enrofloxacin (xacin) with the hybrid surface pyr*n_Hf@GP_BN (where n = 3, 5, 7, or 9) provided insights into the effects of changing the polypyrrole (pyr) chain length on the resulting interactions: xacin_pyr3_Hf@GP_BN, xacin_pyr5_Hf@GP_BN, and xacin_pyr7_Hf@GP_BN respectively to gain more efficient degradation capabilities and the influence of the increase polymer chain. The calculated energy gap decreases due to the increase in LUMO energy experienced upon the addition another of ring, nonetheless when the length of the polypyrrole was further adjusted to seven, the energy gap of the composite increased from 2.184 eV to 2.205 eV which is in the range of semi-conductor to support efficient electron excitation. Results of the molecular dynamic (MD) simulation reveal that while the potential energy of the system decreased for all pyr*n_Hf@GP_BN combinations, the magnitude of the potential energy reduction varied with different pyr chain lengths. Pyr3 exhibited the least reduction of 1310.899 ± 36.119 kcal/mol, followed by 1402.128 ± 38.678 for pyr5, 1511.129 ± 40.494 for pyr7, and 1616.720 ± 43.445 kcal/mol for pyr9, which displayed the most substantial reduction. Longer pyr chains (pyr7 and pyr9) seem to have stronger attractive interactions with enrofloxacin, leading to more significant energy reductions. This indicates that longer pyr chains are more effective in stabilizing the interactions between the antibiotic and the hybrid surface. While the UV-excitation analysis revealed that an increase in the polypyrrole chain length led to a decrease in the wavelength for both the adsorbent and the interactions, decreasing order of exciton binding energy is observed as: 0.602585, 0.606008, and 0.597378 for xacin_pyr3_Hf@GP_BN, xacin_pyr5_Hf@GP_BN, and axacin_pyr7_Hf@GP_BN respectively which is below the 1.9 eV benchmark of efficient materials for photodegradation. The findings could contribute to the broader field of photocatalysis, potentially informing the design of more effective photocatalytic materials. Therefore, research contributes to the development of more efficient methods for antibiotic degradation, with potential applications in environmental remediation.